US3118930A - Process for the preparation of gamma-oxosenecioic acid esters - Google Patents
Process for the preparation of gamma-oxosenecioic acid esters Download PDFInfo
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- US3118930A US3118930A US835852A US83585259A US3118930A US 3118930 A US3118930 A US 3118930A US 835852 A US835852 A US 835852A US 83585259 A US83585259 A US 83585259A US 3118930 A US3118930 A US 3118930A
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- 238000000034 method Methods 0.000 title claims description 19
- 150000002148 esters Chemical class 0.000 title description 14
- 239000002253 acid Substances 0.000 title description 12
- 238000002360 preparation method Methods 0.000 title description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011369 resultant mixture Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical class CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000219109 Citrullus Species 0.000 description 1
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 1
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001746 carotenes Chemical class 0.000 description 1
- 235000005473 carotenes Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- -1 for example Chemical group 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
Definitions
- the -oxosenecioic acid esters according to the invention are useful as intermediates for the synthesis of vitamin A, carotene and others and also useful as a perfume or flavoring agent for foodstuffs on account of its specific fragrance.
- 'y-oxosenecioic acid esters (1V) may be prepared by treating -bromosenecioic acid esters (I) with pyridine to form the pyridinium salt (11), converting the resulting salt into the nitrone by treating it with an alcoholic solution of p-nitrosodialkylaniline, for example, p-nitrosodimethylaniline in the presence of an alkali hydroxide and hydrolyzing the nitrone in the presence of an acid.
- the 'y-oxosenecioic acid esters prepared according to the invention are of higher purity than those produced by the conventional process.
- the process of the invention allows a higher yield of the product than the hitherto known processes.
- the starting 'y-bromosenecioic acid esters may be readily prepared by treating senecioic acid esters with bromine or N-bromosuccinimide.
- esters referred to in the process of the present invention include saturated and unsaturated lower aliphatic and aromatic esters, such as, for example, methyl, ethyl, amyl, octyl, allyl, phenyl, and benzyl esters, etc.
- Example 2 0.7 grams (0.1 mole) of ethyl v-bromosenecioate was dissolved in an amount of benzene. To the resulting solution, a solution of 8 grams (0.1 mole) of anhydrous pyridine in benzene was slowly and dropwise added under stirring with ice-cooling. After completion of the addition, the mixture was heated under reflux for 60 minutes. The solution became red and separated into two layers. After being allowed to cool, the upper layer was decanted and the lower layer of red liquid was washed with benzene. The lower layer of red liquid was covered with a small amount of alcohol and added with an alcoholic solution of 15.0 grams (0.1 mole) of p-nitrosodimethylaniline under ice-cooling.
- Ethyl 'y-oxosenecioate could be similarly prepared even when the paste-like nitrone was subjected to hydrolysis, which was obtained by adding an amount of water to the mother liquor in which the nitrone had been formed, without taking out the nitrone in the form of crystals.
- the ethyl 'y-oxosenecioate obtained by this process was a yellow-colored liquid having a flavor of watermelon. Values of elementary analysis of it corresponded to the calculated values. The infrared spectra of it showed absorptions at 2840 cmr 2720 cmf 1705 cm. due to the aldehyde bond and at 1730 cm? due to the ester bond and at 1645 cm.- due to the double bond between carbon atoms.
- Semicarbazone and 2,4-dinitrophenylhydrazone of this product had melting points of 208 C. and 200 C., respectively.
- the process of preparing a nitrone which comprises preparing a solution by dissolving one mole of a lower alkyl 'y-hromosenecioate in benzene, mixing one mole of anhydrous pyridine with the resulting solution while stirring and cooling, heating the resultant mixture under 25 reflux conditions until the mixture becomes red and forms an upper layer and a lower layer, cooling the mixture, separately treating the lower layer by adding thereto one mole of p-nitrosodimethylaniline in an alcohol solution under cooling conditions, adding to the above-treated lower layer a sodium hydroxide solution while stirring until a crystalline product separates out, and recovering the crystalline product.
- a process as set forth in claim 2 including the additional steps of suspending the crystalline product in ether, adding to the suspension sulfuric acid while stirring and cooling, removing an ether layer from the acidified suspension, and distilling the ether from the other layer to remove a residue.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 3,118,930 PROCESS FOR THE PREPARATION OF 'y-OXOSENECIOIC ACID ESTERS Keiiti Sisido, Sakyoku, Kyoto, Hitosi Nozaki, Wakegun, and Minoru Tuda, Kamikyoku, Kyoto, Japan, assignors to Chugai Seiyaku Kabushiki Kaisha, Chuo-ku, Tokyo, Japan, a corporation of Japan No Drawing. Filed Aug. 25, 1959, Ser. No. 835,852 4 Claims. (Cl. 260-471) This invention relates to a process for the preparation of -oxosenecioic acid esters from 'y-bromosenecioic acid esters with commercial advantages.
The -oxosenecioic acid esters according to the invention are useful as intermediates for the synthesis of vitamin A, carotene and others and also useful as a perfume or flavoring agent for foodstuffs on account of its specific fragrance.
Previously known process for the preparation of y-oxosenecioic acid esters consists in oxidizing -hydroxysenecioic acid esters with activated manganese dioxide to give the end product. However, such process suffers from the disadvantages that the starting material, 'y-hydroxysenecioic acid esters and the oxidizing agent, activated manganese dioxide, are not easily available and that the end product of high purity cannot be obtained. Accordingly this process is not commercially advantageous.
As a result of our many investigations on the processes by which y-oxosenecioic acid esters can be advantageously prepared in high purity, we have found that 'y-oxosenecioic acid esters (1V) may be prepared by treating -bromosenecioic acid esters (I) with pyridine to form the pyridinium salt (11), converting the resulting salt into the nitrone by treating it with an alcoholic solution of p-nitrosodialkylaniline, for example, p-nitrosodimethylaniline in the presence of an alkali hydroxide and hydrolyzing the nitrone in the presence of an acid.
The process of the invention is shown below with chemical equations:
for a lower alkyl group.
The 'y-oxosenecioic acid esters prepared according to the invention are of higher purity than those produced by the conventional process.
The process of the invention allows a higher yield of the product than the hitherto known processes. Furthermore the starting 'y-bromosenecioic acid esters may be readily prepared by treating senecioic acid esters with bromine or N-bromosuccinimide.
The esters referred to in the process of the present invention include saturated and unsaturated lower aliphatic and aromatic esters, such as, for example, methyl, ethyl, amyl, octyl, allyl, phenyl, and benzyl esters, etc.
Example 20.7 grams (0.1 mole) of ethyl v-bromosenecioate was dissolved in an amount of benzene. To the resulting solution, a solution of 8 grams (0.1 mole) of anhydrous pyridine in benzene was slowly and dropwise added under stirring with ice-cooling. After completion of the addition, the mixture was heated under reflux for 60 minutes. The solution became red and separated into two layers. After being allowed to cool, the upper layer was decanted and the lower layer of red liquid was washed with benzene. The lower layer of red liquid was covered with a small amount of alcohol and added with an alcoholic solution of 15.0 grams (0.1 mole) of p-nitrosodimethylaniline under ice-cooling. When cc. of 1 N sodium hydroxide solution was slowly and dropwise added under stirring and the stirring was further continued for about 30 minutes, red-colored crystals separated. This crystalline product was the nitrone of M.P. 90 C. (after recrystallization from benzene-ethyl acetate). This substance is a novel compound. This nitrone was recovered by filtration and suspended in 200 cc. of ether. cc. of *6 N sulfuric acid were slowly added to the suspension with ice-cooling and then stirred for a while. The ethereal layer was subsequently removed and combined with the liquid which had been obtained by extracting the remaining aqueous layer with ether. The combined solution was washed successively with a saturated solution of sodium bicarbonate and Water and dried over anhydrous sodium sulfate. After the drying, the ether was distilled ofi. Distillation of the residue under reduced pressure in nitrogen gas gave 7.7 grams of ethyl 'y-oxosenecioate of B.P. 51-53 C./4.5 mm. Hg and n 1.4597. Yield amounted to 54% on the basis of ethyl y-bromosenecioate.
Ethyl 'y-oxosenecioate could be similarly prepared even when the paste-like nitrone was subjected to hydrolysis, which was obtained by adding an amount of water to the mother liquor in which the nitrone had been formed, without taking out the nitrone in the form of crystals.
The ethyl 'y-oxosenecioate obtained by this process was a yellow-colored liquid having a flavor of watermelon. Values of elementary analysis of it corresponded to the calculated values. The infrared spectra of it showed absorptions at 2840 cmr 2720 cmf 1705 cm. due to the aldehyde bond and at 1730 cm? due to the ester bond and at 1645 cm.- due to the double bond between carbon atoms.
Semicarbazone and 2,4-dinitrophenylhydrazone of this product had melting points of 208 C. and 200 C., respectively.
The process of the present invention can be applied on various esters in a similar manner to the previous example. Results obtained are listed in the following table, together with some properties of the products.
Calculated Found values values -Xoseucci0ate B.P., C./ 11 Yield, Molecular mm. Hg percent formula 0, per- H, per- 0, per- H, percent cent cent cent Methyl 56 5777 1. 4645 48 06115 3- 56. 24 6. 29 56.18 6. 53 Ethyl 51-53/4. 5 1.4597 54 CTI'IXD a 59.14 7. 09 58.83 7. 22 n-Propyl 62.5-63/4. 7 1.4600 C T1203 61.52 7.75 60.03 7.33 n-DutyL 83-84/6 1.4589 46 CoHr-iOa 63. 51 8. 29 62. 54 8. 27 iso-Amyl 82-84/4. 7 1. 4609 010111003.... 65.19 8.75 64. 8. 49
In the table, the yields were calculated on the basis of the v-bromosenecioate used.
What We claim is:
1. A compound of the formula where R and R are each a lower alkyl group. 2
2. The process of preparing a nitrone which comprises preparing a solution by dissolving one mole of a lower alkyl 'y-hromosenecioate in benzene, mixing one mole of anhydrous pyridine with the resulting solution while stirring and cooling, heating the resultant mixture under 25 reflux conditions until the mixture becomes red and forms an upper layer and a lower layer, cooling the mixture, separately treating the lower layer by adding thereto one mole of p-nitrosodimethylaniline in an alcohol solution under cooling conditions, adding to the above-treated lower layer a sodium hydroxide solution while stirring until a crystalline product separates out, and recovering the crystalline product.
3. A process as set forth in claim 2 including the additional steps of suspending the crystalline product in ether, adding to the suspension sulfuric acid while stirring and cooling, removing an ether layer from the acidified suspension, and distilling the ether from the other layer to remove a residue.
4. The process of claim 3 wherein the alkyl 'y-br0mo senecioate is ethyl 'y-bromosenecioate.
References Cited in the file of this patent Beilstein, volume 3, second supp, page 460 (1942).
Claims (3)
1. A COMPOUND OF THE FORMULA
2. THE PROCESS OF PREPARING A NITRONE WHICH COMPRISES PREPARING A SOLUTION BY DISSOLVING ONE MOLE OF A LOWER ALKYL $-BROMOSENECIOATE IN BENZENE, MIXING ONE MOLE OF ANHYDROUS PYRIDINE WITH THE RESULTING SOLUTION WHILE STIRRING AND COOLING, HEATING THE RESULTANT MIXTURE UNDER REFLUX CONDITIONS UNTIL THE MIXTURE BECOMES RED AND FORMS AN UPPER LAYER AND A LOWE LAYER, COOLING THE MIXTURE, SEPARATELY TREATING THE LOWER LAYER BY ADDING THERETO ONE MOLE OF P-NITROSODIMETHYLANILINE IN AN ALCOHOL SOLUTION UNDER COOLING CONDITIONS, ADDING TO THE ABOVE-TREATED LOWER LAYER A SODIUM HYDROXIDE SOLUTION WHILE STIRRING UNTIL A CRYSTALLINE PRODUCT SEPARATES OUT, AND RECOVERING THE CRYSTALLINE PRODUCT.
3. A PROCESS AS SET FORTH IN CLAIM 2 CINCLUDING THE ADDITIONAL STEPS OF SUSPENDING THE CRYSTALLINE PRODUCT IN ETHER, ADDING TO THE SUSPENSION SULFURIC ACID WHILE STIRRING AND COOLING, REMOVING AN ETHER LAYER FROM THE ACIDIFIED SUSPENSION, AND DISTILLING THE ETHER FROM THE ETHER LAYER TO REMOVE A RESIDUE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US835852A US3118930A (en) | 1959-08-25 | 1959-08-25 | Process for the preparation of gamma-oxosenecioic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US835852A US3118930A (en) | 1959-08-25 | 1959-08-25 | Process for the preparation of gamma-oxosenecioic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3118930A true US3118930A (en) | 1964-01-21 |
Family
ID=25270623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US835852A Expired - Lifetime US3118930A (en) | 1959-08-25 | 1959-08-25 | Process for the preparation of gamma-oxosenecioic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3118930A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3274194A (en) * | 1963-03-29 | 1966-09-20 | Miles Lab | Quinazolinedione derivatives |
| US4275220A (en) * | 1979-08-06 | 1981-06-23 | Merck & Co., Inc. | Process for preparing amino acids and esters |
| US5196609A (en) * | 1991-03-05 | 1993-03-23 | Basf Aktiengesellschaft | Preparation of 3-alkoxycarbonyl propenals and 3-dialkoxymethyl propenals |
-
1959
- 1959-08-25 US US835852A patent/US3118930A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3274194A (en) * | 1963-03-29 | 1966-09-20 | Miles Lab | Quinazolinedione derivatives |
| US4275220A (en) * | 1979-08-06 | 1981-06-23 | Merck & Co., Inc. | Process for preparing amino acids and esters |
| US5196609A (en) * | 1991-03-05 | 1993-03-23 | Basf Aktiengesellschaft | Preparation of 3-alkoxycarbonyl propenals and 3-dialkoxymethyl propenals |
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